Production of polymeric compounds



Patented Mar. 30, 1943 PRODUCTION OF POLYMERIC COMPOUNDS Henry Dreyfus,London, England, assignor to Celanese Corporation of America, acorporation of Delaware No Drawing. Application January 30, 1940, Seitrial No. 316,368 In Great BritainJanuary 25,

3 Claims.

This invention relates to improvements in the production of highlypolymeric compounds and the manufacture of artificial filaments andother products therefrom.

I have discovered that synthetic highly molecular substances having alinear structure and containing aminogroups or substituted amino groupsin the side chains, which are very valuable for the production ofartificial filaments, films and other shaped articles, may be obtainedeither by polymerising suitable nitrogen-containing compounds, eitheralone or together with other reactive compounds, or by introducing aminogroups or substituted amino groups into suitable polymeric substanceseither at an intermediate stage of polymerisation or afterpolymerisation has been completed. When the amino or substituted aminogroups are introduced into the polymeric compounds this may be effectedeither before or after conversion of the compounds into shaped articles.

One method of forming the nitrogen-containing polymers of the presentinvention consists in the substitution of hydroxy groups or otherreactive groups or atoms, e. g. halogen atoms, in partially orcompletely polymerised products by amino or substituted amino groups.This method maybe applied to the polymeric products either before orafter their conversion into filaments or other articles. Thesubstitution may be eiiected, for example, byv heating a polymerichydroxy compound with ammonia or a suitable amine in the gaseous orliquid state or the hydroxy compound may be first halogenated, forexample by treating it with gaseous hydrogen chloride, thionyl chloride,or phosphorus pentachloride, and the halogenated product then reactedwith ammonia. or a suitable amine, for example a prinary aliphaticamine. Again, compounds con- ;aining hydroxy groups may be esterifiedwith ;oluene sulphonyl chloride or other aromatic sulphonyl halide andthen reacted with ammonia or an organic base, either alone or in thepresence of a diluent. This method is particularly suitable when it isdesired to carry out the amidation step on filaments or other shapedproducts since the presence of sulphonic acid ester groups in thepolymericcompounds in general improves their solubility in organicsolvents and thus facilitates the production of the shaped articles bythe extrusion of solutions of the polymers through shaping devices intosetting media.

Examples of amines which may be employed in the production of thenitrogen-containing polymers are monoand di-methylamines, ethylaminesand propylamines, ethylene diamine and its a-a-dimethyl derivative,urea, thiourea, cyclohexylamine, piperidine, aniline and p-phenylenediamine. Compounds containing atoms or groups which are more reactivethan the nitrogen-containing groups and which consequently yieldpolymers in which the nitrogen atom is not directly attached to the mainchain may be employed; Halogenated amines, e. g. B-chlorethylamine,p-brom-propylamine, -chlor-butylamine and e-chlor-amylamine, areparticularly valuable for reacting with polymers containing free hydroxygroups or secondary amino groups in the chain. Compounds containing tworeactive groups, e. g. ethylene diamine, are in general most valuablefor the treatment or shaped articles, since they tend to yield insolubleproducts.

The heating of the polymerised products with the nitrogen-containingreactants may be effected at a temperature of e. g. to 200" C. or 250C.. Diluents which may be employed include benzene, toluene, keroseneand anthracene oil. When shaped articles are treated anydiluent employedmust of course be one having no solvent or other detrimental'action onthe articles under the reaction conditions.

The products into which the nitrogen-containing radicles are introducedmay be linear polymers containing in the chain e. g. acid amide groups,ether or thio-ether linkages or second ary or tertiary amino linkages.They may, for instance, be compounds having general formulae of thefollowing types, where R represents a chain of carbon atoms Methods forthe production of such polymers and of other polymers which may betreated by the process of the present invention are described in U. S.applications S.-Nos. 311,570, filed December 29, 1939, 311,932, filedDecember 30, 1939, and 316366 and 316,367, both filed January 30, 1940.

Hydroxy-containing compounds which are amidated, for example, asdescribed above, may have been produced from glycols, glycerine andother trihydroxy alcohols and alcohols containing more than threehydroxy groups, for example erythritol, sorbitol and the sugars, forexample glucose and fructose, and derivatives thereof, for example sugaralcohols and sugar acids. Methods which may be employed for theirproduction a are describedin my co-pending U. 8. application byprocesses described in this application involves the use of ahalogenated substance or other substance containing replaceable groupsor atoms coupled with treatment of the polymerised body with water orother suitable agent to replace the halogen atoms or other reactiveatoms or groups by hydroxy groups, it may be unnecessary to carry outthis step and the production of the nitrogen-containing compounds of'thepresent invention may be effected directly by treatment of thepolymerised body containing halogen atoms or other reactive atoms orgroups with ammonia or an organic base.

As an example of the above method for the production of thenitrogen-containing polymers may be mentioned the treatment of polymericsubstances obtained from mixtures of halogenated ketonic acids andhydroxy aidehydes, for example a mixture of fl-brom-laevulinlc acid andglycol-aldehyde. These substances may be condensed by heating'them,preferably under reduced pressure, and the halogen atoms may then bereplaced by amino or substituted amino groups by heating the productwith ammonia or a suitable organic base. In general the condensation ofa ketonic acid with a hydroxy aldehyde results in the formation of anunsaturated compound arid, if desired, this compound may be furtherhalogenated before amidation.

The nitrogen-containing P ymers of the present invention may also beobtained from starting materials containing two reactive radicals andamino or substituted amino groups. Examples of compounds which may beemployed as starting materials are the amino derivatives of glycerol,erythritol, sorbitol, glucose and other aldoses, fructose and otherketoses, sugar-alcohols, sugar-acids, for example laevulinic acid, andother polyhydroxy alcohols. Self-etherification of these substances oretherification between two or more of these substances may be eflectedby heating them, preferably in the presence of; a suitable catalyst suchas zinc chloride phosphoric acid or hydrogen chloride. Preferably allthe hydroxy groups but two in the sugars or other compounds are blocked,for example by esterification, as otherwise there is a tendency forcross linkages to be formed with the production of polymeric compoundswhich may be too infusible and insoluble to be suitable for themanufacture of artificial filaments and other products. After completionof polymerisation the ester groups may, if desired, be removed byhydrolysis and some or all of the hydroxy groups substituted by amino orsubstituted amino groups.

- Amino derivatives of aldoses, e. s. glucosamine, may also be caused topolymerise by heating them with potassium hydroxide, potassium carbonateor potassium cyanide or with potassium cyanide containing a smallproportion of ammonia.

Highly polymeric compounds may also be produced according to the presentinvention by esterifying amino derivatives of sugars and'otherpolyhydroxy alcohols with dicarboxyiic acids or derivatives thereof, forexample acid halides. Preferably the amino derivatives are firstpartially esterified, for example with acetic anhydride, until only twounesterified hydroxy groups are then reacted with the dlcarboxylicacidor derivatives. Examples of amino derivatives which may beesterified in the above manner are mannamine and galaktamine.

Nitrogen-containing polymeric esters may also be obtained by esterifyingglycols with dlbasic carboxylic acids, one or both of which containsuitable catalyst, for example sulphuric acid or zinc chloride. Insteadof employing the acid a suitable derivative thereof, for example an acidhalide, may be used.

The production of the highly polymeric compounds is, as described above,in general-effected by causing condensation of the reactants by heatingthem at a fairly high temperature, e. g.

150-250 C. or more, and under a low pressure, preferably in the presenceof a suitable catalyst. At least in the later stage the pressure shouldbe reduced to about 5 ms. of mercury or less and this stage may withadvantage be effected in a molecular still. The reaction may be assistedby the presence of condensing agents, e. g. hydrogen chloride, sulphuricacid, or zinc chloride, and diluents or solvents may present. Removal ofwater, hydrohalide acid or other by-product of the reaction may beassisted by passing nitrogen or other inert gas through the reactionmixture. Itisinanycasedesirabletocarryoutpolymerlsation in anoxygen-free atmosphere in order to'avoid or reduce the production ofdark-coloured products. Preferably any traces of oxygen in the inert gasare removed a. g. by passing it through an alkaline solution ofpyrosallol or through sodlumhydrosulphite followed by sodium hydroxide.Preferably after this treatment it is dried, e. g. with calciumchloride, before it enters the reaction vessel.

The reaction is continued-until aproduet is obtained which hasfilamentor film-fanning properties and which has a molecular weight of3,000-4,000 or more. e. g. 7,000, 10,000 or 12,000, and a melting pointof -300 C. or more. Preferably the reaction is stopped while the productis soluble in organic solvents so that filaments andothershapedarticlescanbeproducedbythe shaping and setting of a solution of theproduct in an organic solvent. Further polymerisation of the productmay, if desired, he efiected after the shaped articles are formed. inorder to modify their properties, for example to render them ,insolublein organic solvents.

The production of artificial filaments, films and other shaped articlesfrom the highly polymeric compounds produced according to the presentinvention may be eifected by dissolving the compounds in suitablesolvents, for'example acetone, dioxane, ether or benzene, and extrudingthem through a shaping device into a gaseous or liquid setting medium orby shaping the prodnot itself in a plastic or molten condition.Artiremain, and these partially esterified products 76 ficial filamentsand other products may be stretched during or after their productionwhile in a plastic condition in order to increase their tenacity.

The properties of the highly polymeric products obtained according tothe present invention may be modified by reacting them with suitablesubstances either before or after their conversion into shaped articles.For example, they may be reacted with ethyl chloride, dimethyl sulphateor other alkylating agent, with acidylating agents derived frompolycarboxylic acids, for example phthalyl chloride or succinylchloride, or with dihalogenated paraflins, for example dibromethane.Again, they may be reacted with sulphurcontaining compounds, for examplesulphuryl chloride or thionyl chloride. In general, these reagents,particularly those containing'two reactive groups or atoms, tend toreduce the solubility properties of the highly polymeric compounds andare therefore preferablyemployed for the treatment of the shapedarticles.

Having described my invention, what I desire to secure by Letters Patentis:

1. Process for the production of synthetic linear polymers of highmolecular weight containing ether linkages in the main chain andnitrogen-containing radicles attached to the main chain, which comprisesheating an organic compound which is a partially esterified aminoderivative of a polyhydroxy compound and which contains two free hydroxygroups linked by a chain containing'carbon atoms and a basicnitrogen-containing radicle attached to said chain, heating beingeffected in an oxygen-free atmosphere until a product havingfilament-forming properties is obtained.

2. Process for the production of synthetic 1inear polymers of highmolecular weight containing ether linkages in the main chain andnitrogen-containing radicles attached to the main chain, which comprisesheating an organic compound which is a partially esterified aminoderivative of a polyhydroxy compound and which contains two free hydroxygroups linked by a chain containing carbon atoms and a basicnitrogencontaining radicle attached to said chain, heating beingeffected at a temperature between and 250 C. in an oxygen-freeatmosphere until a product having filament-forming properties isobtained.

3. Process for the production of synthetic liner polymers of highmolecular weight containing ether linkages in the main chain andnitrogen-containing radicles attached to the main chain, which comprisesheating an organic compound which is a partially esterified aminoderivative of a polyhydroxy compound and-which contains two free hydroxygroups linked by a chain containing carbon atoms and a basicnitrogencontaining radicle attached to said chain, heating beingeffected in an oxygen-free atmosphere until a product havingfilament-forming properties and an average molecular weight of at least7,000 is obtained.

HENRY DREYFUS.

CERTIFICATE OF CORRECTION Patent No. 2511;,972. March 50, 19 5.

HENRY DREYFUS.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 1,sec- 0nd column, line 1 6, for the eerie. number "511,952" read--511,95l-; and

' that the said Letters Patent should be read with this correctiontherein that the some may conform to the record of the case in thePatent Office.

Signed. and sealed this 18th day of May, A. 1). 19LL5.

Henry Van Arsdsle, (Seal) Acting Commissioner of Patents.

Peteht No. 2,314,972;

i Certificate of HENRY DREYFUS F v March so, 1943.

It is hereby certified that enor appears in the printed specification ofthe above numbered patent requiring correction as follows: Page 1,second column, line 36,

the formula, for v I -H.oo.NH-1. read 1-1;.- calm-1.;

and that the said Letters Patent should be read virith this correctiontherein heel;

same may conform to the record of the case in the Patent Ofice Signedand sealed this 23rd day of N ovemher, A. D. 1943.

Hnhnir VAR .Ahemtn Q 1 Gammisaabm qf

